Apparatus for generating heat

ABSTRACT

The invention provides an apparatus for heating a liquid, which apparatus comprises:
         a mixing chamber;   dispensing means for dispensing metered amounts of first and second chemical reactants into the mixing chamber to form a reaction mixture so that the chemical reactants undergo an exothermic chemical reaction to generate heat and one or more reaction products;   an electronic control device linked to the dispensing means for controlling the dispensing of the metered amounts of first and second chemical reactants;   one or more pumps for moving the chemical reactants and reaction mixture around the apparatus;   a heat exchanger having an inlet and an outlet for the reaction mixture and an inlet and an outlet for the said liquid, so that when said liquid passes through the heat exchanger it is heated by heat transfer from the reaction mixture;   one or more monitoring stations for monitoring one or more physical or chemical parameters of the reaction mixture; the monitoring stations being arranged to communicate with the electronic control device; and   a waste outlet for removing spent reaction mixture from the apparatus;   wherein the mixing chamber, heat exchanger and the one or more monitoring stations are connected so as to form a loop; and wherein the electronic control device is programmed to cause the reaction mixture to be circulated around the loop at least twice, and optionally to cause the dispensing means to dispense further metered amounts of first and/or second chemical reactants into the mixing chamber; and/or to cause a proportion of the reaction mixture to be ejected through the waste outlet, in order to control the temperature of the reaction mixture passing through the heat exchanger.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a national stage filing under section 371 ofInternational Application No. PCT/GB2010/001884, filed on Oct. 7, 2010,and published in English on Apr. 14, 2011, as WO 2011/042702, and claimspriority to British Application No. 0917546.4 filed on Oct. 7, 2009. Theentire disclosures of each of the prior applications are herebyincorporated herein by reference.

This invention relates to an apparatus for generating heat for use in aheating system for liquids such as water.

BACKGROUND OF THE INVENTION

It is well known that many chemical reactions are exothermic, i.e. theyproduce heat, and examples of such reactions include acid-basereactions.

U.S. Pat. No. 4,325,355 describes a heating system in which anexothermic reaction between a solid metal and a solution takes place ina reactor containing a heat exchanger. In the specific reaction systemdescribed, aluminium pieces are lowered into a solution of sodiumhydroxide solution. During the reaction between aluminium and sodiumhydroxide solution, the aluminium is converted to aluminium hydroxidewith the evolution of hydrogen gas. The aluminium hydroxide reacts withthe sodium hydroxide to form sodium aluminate.

DE 3539710 describes a small scale heating system comprising an outerpouch containing an inner pouch partitioned to form two chamberscontaining reactive chemicals. Pressurising the pouch (for example bykneading) causes the partition wall to rupture allowing the two reactivechemicals to react to produce heat. The reactive chemicals can be sodiumhydroxide and acetic anhydride. The heating system of DE 3539710 isdescribed as being particularly useful for warming hands and feet.

GB 2381187 discloses a method and apparatus for cleaning a surface. Aspart of the cleaning process, a cleaning solution is heated by themixing of chemicals in an exothermic reaction.

WO 86/01880 describes a heating system that can be used for domesticwater heating and which involves a multistage process comprising a firstheat exchange step in which heat extracted from sea water is used tovapourise a liquefied gas such as ammonia. The ammonia vapour thenpasses to a second stage where it reacts either with sodium carbonatesolution or carbon dioxide in an exothermic process, the heat from whichis extracted to heat domestic water.

U.S. Pat. No. 4,044,821 describes an energy conversion and storagesystem in which chemical compounds such as ammonia or metal hydrides aredecomposed using energy from, for example, a solar energy device. Thedecomposition products can be recombined in a later step to producechemical energy.

WO 2004/040645 discloses a microfluidic heat exchanger for providingsmall scale heating and cooling control using exothermic and endothermicchemical reactions. The addition of sulphuric acid to water is disclosedas an example of an exothermic heating source.

U.S. Pat. No. 3,563,226 describes a heating system intended for useunderwater or in oxygen-free environments in which an oxidiser such aspure oxygen is reacted with a pyrophoric material such as phosphorus.

U.S. Pat. No. 7,381,376 discloses steam/vapour generators in which thesource of the heat is an exothermic chemical reaction.

DE 3819202 describes a system of heat storage using molten salts.

U.S. Pat. No. 4,303,541 describes latent heat storage devices that makeuse of saturated solutions of salts. The salts are formed by thereaction of an acid and a base, and there is a passing reference to thepossibility that the heat generated in the reaction may be usedelsewhere.

My earlier patent application WO2008/102164 discloses a method andapparatus for producing a supply of a heated fluid (e.g. water) whereinthe method comprises passing the fluid through a heat exchanger unitwhere it is heated by a heat source which derives its heat from theexothermic reaction of two or more chemical reactants.

The present invention provides an improved apparatus for making use ofthe heat generated by exothermal chemical reactions to heat liquids suchas the water in a water supply.

SUMMARY OF THE INVENTION

In a first aspect, the invention provides an apparatus for heating aliquid, which apparatus comprises:

a mixing chamber;

dispensing means for dispensing metered amounts of first and secondchemical reactants into the mixing chamber to form a reaction mixture sothat the chemical reactants undergo an exothermic chemical reaction togenerate heat and one or more reaction products;

an electronic control device linked to the dispensing means forcontrolling the dispensing of the metered amounts of first and secondchemical reactants;

one or more pumps for moving the chemical reactants and reaction mixturearound the apparatus;

a heat exchanger having an inlet and an outlet for the reaction mixtureand an inlet and an outlet for the said liquid, so that when said liquidpasses through the heat exchanger it is heated by heat transfer from thereaction mixture;

one or more monitoring stations for monitoring one or more physical orchemical parameters of the reaction mixture; the monitoring stationsbeing arranged to communicate with the electronic control device; and

a waste outlet for removing spent reaction mixture from the apparatus;

wherein the mixing chamber, heat exchanger and the one or moremonitoring stations are connected so as to form a loop; and wherein theelectronic control device is programmed to cause the reaction mixture tobe circulated around the loop at least twice, and optionally to causethe dispensing means to dispense further metered amounts of first and/orsecond chemical reactants into the mixing chamber; and/or to cause aproportion of the reaction mixture to be ejected through the wasteoutlet, in order to control the temperature of the reaction mixturepassing through the heat exchanger.

Particular and preferred aspects and embodiments of the invention are asdescribed below and as set out in the claims appended hereto.

In the apparatus of the invention, the mixing chamber, heat exchangerand the one or more monitoring stations are connected so as to form aloop; and the electronic control device is programmed to cause thereaction mixture to be circulated around the loop at least twice. Whenthe apparatus is started up, the dispensing means dispenses initialcharges of the two chemical reactants into the mixing chamber. The tworeactants react exothermically to give rise to a heated reaction mixturewhich may contain only reaction products or a mixture of reactants andreaction products depending on the rate constant for the chemicalreaction in question and the concentrations of the reactants. The heatedreaction mixture is then directed through the heat exchanger, eitherdirectly or via one or more other system components such as a monitoringstation and/or a mixer and/or a pump. In the heat exchanger, the heatedreaction mixture transfers heat to a liquid (e.g. water for a waterheating system) passing through the heat exchanger.

While passing through the heat exchanger, the reaction mixture may havegiven up all of its heat; i.e. the temperature of the reaction mixturemay have returned to ambient temperature. However, an equally common (ifnot more common) scenario is that the reaction mixture may have given uponly a proportion of its heat to the liquid in the heat exchanger.Furthermore, in some cases, the reaction between the first and secondreactants may not have gone to completion and there may consequently beunreacted reactants in the reaction mixture. In such cases, it would bewasteful and inefficient to discharge the reaction mixture to waste.Instead, the apparatus of the invention is set up so that the reactionmixture moves in a loop and is returned to the mixing chamber. At thisstage, depending upon the temperature difference between the reactionmixture and a predetermined target temperature required to heat theliquid passing through the heat exchanger, further charges of the firstand/or second reactants may be dispensed into the mixing chamber togenerate more heat. Thus the electronic controller may be programmedsuch that if the temperature of the reaction mixture exceeds a certainvalue, no further charges of reactants are introduced into the mixingchamber. Conversely, if the temperature of the reaction mixture hasdropped below a predetermined value, the electronic controller promptsthe dispensing means to dispense additional charges of one or bothreactants. The reaction mixture, supplemented as required with furtherreactants is then circulated around the system for a second time. Thus,in the apparatus of the present invention, the reaction mixture isrecycled one or more times after it has completed its initial passagearound the loop.

By recycling the reaction mixture around the loop, the maximum amount ofheat can be extracted from the reaction mixture.

Typically, the reaction mixture is circulated around the loop betweentwo and twenty times, for example from three to twelve times.Preferably, the reaction mixture is circulated around the loop at leastthree times, and more usually at least four times.

The recycling of the reaction mixture around the loop and the additionof further charges of the two reactants are controlled by an electroniccontroller (a computer or microprocessor). The electronic controller islinked (electronically or wirelessly) to each of the monitoring stationsand receives feedback on key physical and chemical parameters of thereaction mixture. Monitoring stations can be located at a number ofpositions in the loop.

In one embodiment, a monitoring station for monitoring one or morephysical or chemical parameters of the reaction mixture is locateddownstream of the mixing chamber and upstream of the heat exchanger.

Alternatively or additionally, a monitoring station for monitoring oneor more physical or chemical parameters of the reaction mixture can belocated downstream of the heat exchanger and upstream of the mixingchamber.

A variety of different physical and chemical parameters may be monitoredat the monitoring station, depending on the nature of the exothermicchemical reaction.

Typically, at least one monitoring station measures the temperature ofthe reaction mixture. Preferably the temperature is monitored by each ofa plurality (e.g. two) of monitoring stations.

When the chemical reactants are an acid and a base, it is preferred thatat least one monitoring station (and preferably two or more monitoringstations) measures the pH of the reaction mixture. Information fed backto the electronic controller is then used to determine whether furtheracid or base needs to be added to the mixture.

As the concentrations of reactants and reaction products in the reactionmixture increases, so the viscosity of the reaction mixture may increaseleading to a reduction in the flow rate or an increase in the energyneeded to pump the reaction mixture around the loop. Therefore, amonitoring station may comprise means for measuring the flow rate and/orviscosity of the reaction mixture.

In one preferred embodiment of the invention, the one or more physicalor chemical parameters monitored by the monitoring stations are selectedfrom the pH, temperature, flow rate and viscosity of the reactionmixture.

In another embodiment, the monitoring one or more monitoring stationseach measure both the temperature and pH of the reaction mixture.

In order to enable efficient mixing of the reactants and thereby assistthe reaction between the reactants to proceed to completion one or morefurther mixers (e.g. static in-line mixers) may be provided at variouslocations around the loop. The use of further in-line mixers isparticularly beneficial at higher flow rates around the loop whenmaximal mixing is required in the shortest time.

For example, in one embodiment, a monitoring station is providedimmediately downstream of the mixing chamber and an in-line mixer isinterposed between the monitoring station and the heat exchanger.

In another embodiment, a monitoring station is provided downstream ofthe heat exchanger and upstream of the mixing chamber and an in-linemixer is located in the loop downstream of the monitoring station andupstream of the mixing chamber.

The apparatus is provided with a waste outlet so that spent (orsubstantially spent) reaction mixture can be removed from the system tomake room for the addition of fresh reactants. The waste outlet ispreferably linked to the electronic controller so that a proportion ofthe reaction mixture can be sent to waste when one or more physical orchemical parameters of the reaction mixture falls below or exceeds apredetermined value.

For example, if all of the heat has been extracted from the reactionmixture in the heat exchanger (i.e. the temperatures of the reactionmixture and the liquid passing through the heat exchanger aresubstantially the same), a proportion of the reaction mixture may besent to waste to enable fresh reactants to be introduced into the mixingchamber to generate more heat.

Furthermore, as the reaction progresses, the viscosity of the reactionmixture will typically increase and the electronic controller mayinstruct the waste outlet to open to allow release of a proportion ofthe reaction mixture once the viscosity has exceeded a predeterminedvalue.

In many cases, the recycling of the reaction mixture may lead to theconcentrations of reaction products increasing to the point where asaturated solution is formed and reaction products begin to precipitateor crystallise out of solution. When the reactants are acids and bases,salts may typically begin to precipitate or crystallise out of solutionafter about three or four cycles. A settling tank may therefore beprovided at or adjacent the waste outlet to allow solid material tosettle out of the reaction mixture before removal through the wasteoutlet.

The waste outlet is typically located downstream of the heat exchangerand, in one embodiment, is disposed at or immediately adjacent amonitoring station downstream of the heat exchanger.

In one embodiment of the invention, the electronic control device isprogrammed to cause a proportion of the reaction mixture to be ejectedthrough the waste outlet when the viscosity of the reaction mixtureexceeds a predetermined value and/or the flow rate of the reactionmixture around the loop is less than a predetermined value.

The apparatus of the invention may be operated for a period of time overwhich a supply of heated liquid is required and the electroniccontroller may be programmed or otherwise set up to provide a definedamount of heat during the operating period. Typically the electroniccontroller will contain means for selecting a desired temperature(target temperature) for the liquid during the period of time over whichthe apparatus is operated.

At the end of the period of operation, the spent reaction mixture istypically ejected from the system and the loop and optionally othercomponents of the system are flushed (e.g. with water) to remove anyresidual traces of reaction products.

After flushing, the apparatus, or at least the loop, may be drained downin readiness for the next heating session.

Accordingly, in one embodiment, the electronic control device isprogrammed to provide a flushing step at the end of a predeterminedperiod of heating, the flushing step serving to flush out of theapparatus any residual reaction mixture. Preferably, the electroniccontrol device is programmed to provide a drainage step following theflushing step.

The chemical reactants are typically contained within storage containersforming part of the apparatus. Preferably the chemical reactants areintroduced into the mixing chamber via the dispensing means in the formof solutions, on the basis that it is easier to provide accuratemetering of the amounts of reactants added when they are in liquid formthan when they are in solid form.

Some chemical reactants may be stored in their storage containers in theform of solids and then dissolved to form solutions immediately beforepassing through the dispensing means and being introduced into themixing chamber. This is particularly preferred where the solid form ofthe reactant is stable and has good handling characteristics and wherethe dissolution of the reactant in the solvent is an exothermic process.In such a case, the heat generated by the dissolution of the reactantcan be made use of, for example to raise the temperature of the otherreactant so that the temperatures of the two reactants as they passthrough the dispensing means are similar or substantially identical. Toallow transfer of heat between the two reactant solutions, a second heatexchanger may be provided upstream of the dispensing means.

Accordingly, in one preferred embodiment of the invention, the apparatuscomprises a second heat exchanger, the second heat exchanger beinglocated externally of the loop and upstream of the dispensing means, andhaving an inlet and an outlet for the first chemical reactant and aninlet and an outlet for the second chemical reactant, so that heat maybe exchanged between the first and second chemical reactants withoutmixing of the reactants.

A mixer may be provided upstream of the second heat exchanger, anddosing means provided for introducing into the mixer one of the firstand second reactants and a solvent therefor.

The dispensing means may comprise individual dispensing devices for eachof the reactants or a unitary metering and dispensing device throughwhich both reactants pass. The dispensing device may also have an inletfor receiving recycled reaction mixture and an outlet for dispensingrecycled reaction mixture into the mixing chamber. Thus the dispensingdevice may form part of the loop.

In one embodiment, the first and second chemical reactants are an acidand a base.

Preferably the acid is selected from mineral acids and carboxylic acids.

The acid may be selected from acids having a pka value of >0, moretypically >2 and preferably >3, e.g. a pKa in the range 3 to 7.

The acid may be a polybasic acid, one preferred acid being citric acid.

The base is preferably selected from alkali metal hydroxides, alkalineearth metal hydroxides, alkali metal carbonates, alkaline earth metalcarbonate, alkali metal bicarbonates, alkaline earth metal bicarbonate,and amines, and mixtures thereof.

Examples of alkali metal hydroxides are lithium hydroxide, sodiumhydroxide and potassium hydroxide.

Examples of alkaline earth metal carbonates are magnesium hydroxide andcalcium hydroxide.

Examples of alkali metal bicarbonates are sodium bicarbonate andpotassium bicarbonate.

Particular bases are basic amines and in particular mono-, di- andtrialkylamines and hydroxy derivatives thereof.

One group of preferred bases consists of mono-, di- and trialkylaminesand hydroxy derivatives thereof in which each alkyl group contains from1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms and mostpreferably 1 or 2 carbon atoms. Such bases include methylamine,dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine,monoethanolamine and diethanolamine.

In one embodiment, the base is sodium hydroxide.

In another embodiment, the base is a mixture of sodium, hydroxide andmonoethanolamine.

In another embodiment, the first reactant is aluminium and the secondreactant is a metal hydroxide, preferably an alkali metal hydroxide(such as sodium hydroxide or potassium hydroxide) and most preferablysodium hydroxide.

Preferably the aluminium is in powder form.

In another aspect, the invention provides an apparatus for heating aliquid, which apparatus comprises:

a first storage container containing a first chemical reactant whichcomprises aluminium in powder form;

a second storage container containing a second chemical reactant whichcomprises an alkali metal hydroxide;

a mixing chamber;

dispensing means for dispensing metered amounts of the first and secondchemical reactants the first and second storage containers into themixing chamber to form a reaction mixture so that they undergo anexothermic chemical reaction to generate heat and reaction products, oneof the reaction products being hydrogen gas;

an electronic control device linked to the dispensing means forcontrolling the dispensing of the metered amounts of first and secondchemical reactants;

one or more pumps for moving the chemical reactants and reaction mixturearound the apparatus;

a heat exchanger having an inlet and an outlet for the reaction mixtureand an inlet and an outlet for the said liquid, so that when said liquidpasses through the heat exchanger it is heated by heat transfer from thereaction mixture;

one or more monitoring stations for monitoring one or more physical orchemical parameters of the reaction mixture; the monitoring stationsbeing arranged to communicate with the electronic control device; and

a waste outlet for removing one or more non-gaseous reaction productsfrom the apparatus;

an outlet for removing hydrogen gas from the apparatus;

wherein the mixing chamber, heat exchanger and the one or moremonitoring stations are connected so as to form a loop; and wherein theelectronic control device is programmed to cause the reaction mixture tobe circulated around the loop at least twice, and optionally to causethe dispensing means to dispense further metered amounts of first and/orsecond chemical reactants into the mixing chamber; and/or to cause aproportion of the reaction mixture to be ejected through the wasteoutlet, in order to control the temperature of the reaction mixturepassing through the heat exchanger.

The aluminium is preferably introduced into the mixing chamber in theform of an aqueous slurry. Preferably the aluminium powder is mixed withwater to form a slurry immediately before entry into the mixing chamber.

The alkali metal hydroxide is typically sodium hydroxide or potassiumhydroxide and preferably is sodium hydroxide.

The reaction between aluminium and aqueous sodium hydroxide initiallyconsumes sodium hydroxide and produces sodium aluminate which undergoesa decomposition reaction when its concentration exceeds the saturationlimit. A crystalline precipitate of aluminium hydroxide is produced withthe regeneration of the alkali. Overall only aluminium and water areconsumed, so that the role of the alkali in this process can be seen asbeing catalytic.

A first waste outlet for removing one or more non-gaseous reactionproducts from the apparatus is typically located between the mixingchamber and the heat exchanger. Precipitated crystalline aluminiumhydroxide (or other precipitated reaction product) is preferably removedat the said waste outlet. Accordingly, the waste outlet may be providedwith a filter for filtering off precipitated reaction product or asettling chamber in which precipitated reaction product can settle outand be withdrawn through the waste outlet.

Although crystalline aluminium hydroxide (or other precipitated reactionproduct) may be removed at the waste outlet, further precipitation mayoccur downstream of the waste outlet as the reaction mixture cools down.In order to prevent precipitation, a third chemical reactant may beintroduced into the apparatus downstream of the first waste outlet andupstream of the heat exchanger.

The third chemical reactant may be an alkali metal borohydride such assodium borohydride. Sodium borohydride reacts with the aluminiumhydroxide to generate heat and produce further hydrogen. The heatingboost provided by the reaction prevents precipitation of reactionproducts from taking place in the heat exchanger.

Hydrogen produced by the reaction can either be separated by means of aliquid-gas separator disposed upstream of the heat exchanger or can beremoved when the reaction mixture is recycled back to the mixingchamber.

The apparatuses of the invention are particularly useful for heatingwater.

Accordingly, the apparatus may form part of a domestic water heatingsystem or an industrial or commercial water heating system.

In one embodiment, the apparatus forms part of a water heating systemintended to provide water for central heating or sanitation purposes.

In another embodiment, the apparatus forms part of a water heatingsystem for a swimming pool.

In another aspect, the invention provides a method of heating a liquidwhich method comprises passing the liquid through the heat exchanger ofan apparatus as defined herein.

A substantial advantage of the apparatus of the invention is that itprovides a very efficient means for heating a liquid such as waterwhereby heating losses to the external environment are minimised. Heatlosses may be minimised still further by insulating the components ofthe apparatus in conventional fashion.

A further advantage of the apparatus of the invention is that it can beused in locations where mains electricity or mains gas supplies are notavailable or are restricted. Thus, although electrical power is requiredto operate the apparatus, the amount of power required is relativelysmall and can therefore be supplied by renewable resources such as awind turbine or solar power.

The invention will now be illustrated in more detail (but not limited)by reference to the specific embodiment shown in the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an apparatus according to one embodimentof the invention.

FIG. 2 is a schematic view of an apparatus according to a secondembodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As shown in FIG. 1, an apparatus for producing heat according to oneembodiment of the invention comprises storage containers 2 and 4, eachof which contains a component of an exothermic chemical reaction system.Storage container 2 is connected via pipes 3 a and 3 b to a heatexchanger 6, an optional static in-line mixer 8 being located betweenthe container 2 and the heat exchanger 6.

Container 4 is connected by pipe 10 to a first dosing/metering station12. Dosing/metering station 12 has an inlet 14 for receiving water froma water supply (represented schematically by the number 16) and pair ofoutlets which are connected via pipes 18 and 20 to a static in-linemixer 22 and thence via pipe 24 to the heat exchanger 6 (whichconstitutes the second heat exchanger as hereinbefore defined).

The heat exchanger 6 has two outlets, one for each of the components ofthe exothermic reaction system (they do not mix in the heat exchanger),the two outlets leading via pipes 26 and 28 to the main dosing/meteringstation 30 (which constitutes the dispensing means as hereinbeforedefined). The main dosing/metering device 30 has a pair of outlets (onefor each component of the exothermic reaction system) which lead viapipes 32 and 34 to a clear pipe static mixer 36 (which constitutes themixing chamber as hereinbefore defined).

The static mixer is 36 connected via a single outlet via pipe 38 to afirst product monitoring station 40 which in turn is linked by pipes 42a and 42 b and static in-line mixer 44 to the main heat exchanger 46.The first product monitoring station 40 is linked electronically bycable 41 to the main dosing/metering station 30. As an alternative tobeing linked by cable, a wireless connection to the dosing/meteringstation 30 could be provided instead.

The heat exchanger 46 has an inlet 48 and an outlet 50 for water and anoutlet for the products of the exothermic chemical reaction. Outlet 52leads via pipe 54, static in-line mixer and pipe 58 to a second productmonitoring station 60. The second product monitoring station 60 has anoutlet that leads back via pipes 62 and 64 and static in-line mixer 66to the main dosing/metering station 30. The second product monitoringstation 60 also has a waste outlet 68 for the removal of spentreactants. The second product monitoring station 60 is also linkedelectronically by cable 61 (or wirelessly) to the main dosing/meteringdevice 30.

Each of the component parts of the system shown in FIG. 1 is thermallyinsulated to reduce or prevent heat loss, with the exception in certaincases of the elements of the system preceding the first heat exchanger6. Thus, for example, in cases where the first step in the processinvolves dissolving one of the chemical reactants in a solvent such aswater, and the dissolution process is endothermic, the container forthat chemical reactant and the associated pipework leading to the firstheat exchanger 6 may be left uninsulated to allow the solution ofdissolved reactant to take in heat from its surroundings and come up toambient temperature.

The system illustrated in FIG. 1 is particularly suitable for use ingenerating and using heat from the endothermic reaction between an acidand a base, although it may be used and/or adapted for use with othercombinations of chemical reactants.

Thus, with reference to the particular example of the reaction of citricacid with sodium hydroxide or a mixture of sodium hydroxide andmonoethanolamine, the heat generating system of the invention functionsin the following manner.

Sodium hydroxide pellets from the container 4 are conveyed by eccentricscrew pump (not shown) along pipe 10 to the first dosing/meteringstation 12 where a metered quantity of the pellets is moved by aprogressive cavity pump (not shown) along outlet pipe 18 to the staticin-line mixer 22. At the same time, a charge of monoethanolamine (forexample in an amount corresponding to about 1% to 15% by weight relativeto the sodium hydroxide) is conveyed from a reservoir (not shown)through the first dosing/metering station 12 and along pipe 18 to thein-line mixer. Water from source 16 enters the dosing/metering station12 through inlet 14 and a metered amount is then directed along outletpipe 20 to the static in-line mixer 22 where it is mixed with the sodiumhydroxide and ethanolamine.

The reaction between the sodium hydroxide and the water is exothermicand represents the first heat generating stage of the process. Theresulting warm aqueous solution of sodium hydroxide and ethanolamine isthen directed along pipe 24 to the heat exchanger 6.

An aqueous solution of citric acid from the container 2 is directedalong pipes 3 a and 3 b via static in-line mixer 8 to the first heatexchanger where it exchanges heat with (but does not mix with) the flowof sodium hydroxide and ethanolamine solution. The transfer of heatbetween the two streams of reactants results in the temperatures of thetwo streams moving towards parity.

After exiting the first heat exchanger 6 and moving along pipes 26 and28 respectively, the streams of citric acid solution and sodiumhydroxide/ethanolamine solution enter the main dosing/metering station30.

At the start of the heat generation process, the dosing/metering station30 dispenses charges of citric acid solution and sodiumhydroxide/monoethanolamine solution in a 1:3 molar ratio of acid:basealong pipes 32 and 34 into the clear pipe static mixer 36. An exothermicreaction between the citric acid and sodium hydroxide takes place in themixer 36 to form citrate salts and generate heat. The warm reactionmixture is then passed along pipe 38 and into the first productmonitoring station 40 where the pH and temperature of the mixture aremeasured and the measurements sent back along cable 41 to a anelectronic computerised controller forming part of the dosing/meteringstation 30. The product monitoring station 40 may also include a flowmeter for measuring the flow rate of the reaction mixture.

After the product monitoring station 40, the reaction mixture isdirected via pipes 42 a and 42 b and static in-line mixer 44 to the mainheat exchanger 46. At the heat exchanger 46, heat is transferred fromthe warm reaction mixture to a stream of water for a warm/hot watersupply (e.g. water for a domestic hot water supply or a heated swimmingpool).

Having given up all or some of its heat, the reaction mixture leaves theheat exchanger 46 and travels via pipe 54, static in-line mixer and pipe58 to the second product monitoring station 60. At monitoring station60, the pH and temperature are again measured and the measurements sentalong cable 61 to the controller at the dosing/metering station 30.

After leaving the second product monitoring station 60, the reactionmixture is directed through pipe 62, static in-line mixer and pipe 64back to the main first dosing/metering station 30 to complete a firstcycle.

During its progress around the first cycle, the sodium hydroxide andmono-ethanolamine may have undergone complete reaction with the citricacid or only partial reaction. The reaction mixture may thereforecontain unreacted acid or base as well as dissolved citrate salt. Inaddition, the temperature of the reaction mixture may still be higherthan the target temperature of the water passing through the heatexchanger.

At the end of the first cycle therefore, depending on the temperatureexcess (with respect to the target temperature for the water), and thepH of the reaction mixture, further charges of citric acid solutionand/or sodium hydroxide/monoethanolamine may be dispensed from the maindosing/metering station 30 into the pipes 32 and 34 leading to the mixer36. Alternatively, the controller may be programmed such that if thetemperature differential between the reaction mixture and the targettemperature for the water passing through the main heat exchanger 46exceeds a predetermined value, no additional acid or base is dispensedinto the mixer 36.

Subsequently, if the product monitoring stations 40 and 60 detect thatthe temperature of the reaction mixture has fallen below a predeterminedvalue necessary to heat the water entering the main heat exchanger 46 tothe target temperature, further charges of acid and base may bedispensed into the mixer 36.

Top up additions of acid and base may be made as and when necessary inorder to maintain the reaction mixture at the desired temperature.

By recycling the reaction mixture and carefully monitoring the pH andtemperature of the mixture and adding further charges of acid and baseas needed, the greater part of the heat generated from the exothermicreaction of the citric acid and the sodium hydroxide/ethanolamine can beextracted and transferred to the water passing through the main heatexchanger. Because the system is well insulated, very little heat islost to the surroundings.

The system illustrated in FIG. 1 is provided with one or more flowmeters (not shown) which may form part of the product monitoringstations 40 and 60 or may be located at other points in the circuit.

During each heat-generating session, the reaction mixture may berepeatedly circulated around the system, for example at least five timesand more usually up to about ten times or more. At intervals, spentreaction mixture may be discharged through the waste exit 68 where itmay be collected for recycling and reprocessing. The mixture may bedischarged as and when necessary to create room for more acid or base tobe introduced into the system.

After several cycles, the reaction mixture may reach the state of asaturated solution and citrate salts may begin to precipitate orcrystallise out of solution. This process may be accelerated as heat isremoved from the reaction mixture by the main heat exchanger 46. Thesecond product monitoring station may therefore incorporate or be linkedto a settling tank or chamber (not shown) in which precipitated orcrystallised salts can settle out thereby enabling them to be removedmore easily. In order to minimise heat loss from the system, the spentreaction mixture and precipitated or crystallised salts are preferablyremoved at a time point when the temperature of the reaction mixture isat or near its coolest value.

The heating process is continued as described above for a requiredperiod of time (e.g. the time necessary to heat a desired volume ofwater to a given target temperature), and the system is then flushedwith clean water to remove salts and any residual acid and base. Afterflushing, the system is automatically drained down (e.g. through thewaste outlet 68) to leave the system ready for the next heating session.

The heating system of the invention functions as a partially closedsystem. When starting up the process, air is driven out of the systemthrough valves or air vents (not shown) which are then closed to preventloss of the reaction mixture. The reaction mixture is then continuouslyrecycled around the system, the system being opened at intervals toallow the addition of further charges of acid and base and to permitspent reaction mixture to be discharged to waste. By keeping the systemclosed between additions of reactants and the discharge of spentreaction mixture, substantially all available heat can be extracted fromthe system. This represents a substantial advantage of the method andapparatus of the invention and provides a contrast with heating systemssuch as oil or gas burning systems where much of the heat produced islost with the flue gases.

An apparatus according to a second embodiment of the invention isillustrated in FIG. 2.

As shown in FIG. 2, the apparatus comprises a first storage container102 containing aluminium powder linked via pipe 104 to a preliminarymixing tank 106 fitted with a stirrer 108. The preliminary mixing tankis connected via pipe 110 and pump 112 to the mixing chamber 114.

A second storage container 116 containing concentrated aqueous sodiumhydroxide is connected via pipe 118 and pump 120 to the mixing chamber114.

The mixing chamber 114 has an outlet at its lower end connecting viapipe 122 to a first waste outlet chamber 124 having a waste outlet 126leading via pipe 128 to a waste tank 130. The waste outlet chamber 124is provided with a scraper device comprising a plurality of blades 132mounted on a rotating spindle driven by a motor 134.

The waste outlet chamber 124 has a further outlet 136 connected to pipe138 which leads via pump 140 and third reactant dosing station 142 tothe heat exchanger 144. The heat exchanger is connected by pipe 146 tothe recycling inlet 148 of the mixing chamber 114.

At the upper end of the mixing chamber 114 is a hydrogen gas vent whichis connected via pipe 150 to a burner 152.

In use, a metered amount of aluminium powder from the first storagecontainer 102 is charged into the preliminary mixing tank 106 and water(water inlet not shown) is added. The mixture is stirred vigorously toform a slurry and rapidly pumped along pipe 106 to the mixing chamber114. By adding the water to the aluminium to form the slurry immediatelyprior to charging it into the mixing chamber, loss of heat due to anyinitial reaction between the aluminium and water is minimised.

A metered amount of concentrated sodium hydroxide solution from thesecond storage container 116 is pumped via pipe 118 and pump 120 intothe mixing chamber where it reacts with the aluminium.

Hydrogen gas produced by the reaction of the aluminium and the sodiumhydroxide is vented through the outlet at the upper end of the mixingchamber 114 and is conveyed through pipe 150 to the burner 152 where itis combusted to provide an additional source of heat for the mixingchamber.

After allowing reaction between the sodium hydroxide and aluminium totake place in the mixing chamber 114, the reaction mixture is allowed topass out of the outlet in the lower end of the mixing chamber along pipe122 to the waste outlet chamber 124. In the waste outlet chamber,precipitated aluminium hydroxide settles to the bottom of the chamberand is drained away via waste outlet 126 and pipe 128 to the waste tank130. Any aluminium hydroxide crystallising on the walls of the chamber124 is scraped off by the motorised rotating scraper device 132, 134 andallowed to fall to the bottom of the chamber.

The reaction mixture exits the waste outlet chamber through outlet 136and is pumped by pump 140 along pipe 138 to the heat exchanger 144 wherethe heat is used to heat water flowing through the heat exchanger.

Although the pipework is fully insulated, there is likely to be someheat loss between the waste outlet chamber and the heat exchanger andthis may lead to further aluminium hydroxide precipitating out in thepipes and in the heat exchanger thereby leading to blockages. In orderto prevent this from occurring, a third reactant is introduced atstation 142. The third reactant in this case is sodium borohydride whichreacts with the aluminium hydroxide.

The heat generated by the reaction is sufficient to maintain thetemperature at a level whereby supersaturation and precipitation doesnot occur. In addition, further hydrogen is generated which can eitherbe extracted at a gas-liquid separator (not shown) or removed from themixture once the reaction mixture re-enters the mixing chamber 114through recycling inlet 148.

Once the reaction mixture has re-entered the mixing chamber, a furthercharge of aluminium is introduced into the chamber to continue thecycle. Although the sodium hydroxide functions in a catalytic manner,some of the sodium hydroxide will typically be lost to waste at thefirst waste outlet chamber 124. A further charge of sodium hydroxide maytherefore be added from storage container 116.

As with the embodiment of FIG. 1, the apparatus of FIG. 2 is typicallyprovided with one or more product monitoring stations for monitoring oneor more physicochemical properties of the reaction mixture (e.g. the pHor the temperature) to determine when further reactants need to beadded. The apparatus may be set up to dispense further charges ofreactants automatically or may provide a prompt to the user to make thenecessary adjustments manually.

As with the apparatus of FIG. 1, the reaction mixture is pumped around apartially closed loop and is recycled a number of times in order toallow optimal extraction of heat before discharging to waste.

The embodiments described above and illustrated in the accompanyingfigures and tables are merely illustrative of the invention and are notintended to have any limiting effect. It will readily be apparent thatnumerous modifications and alterations may be made to the specificembodiments shown without departing from the principles underlying theinvention. All such modifications and alterations are intended to beembraced by this application.

1-41. (canceled)
 42. An apparatus for heating a liquid, which apparatuscomprises: a mixing chamber; dispensing means for dispensing meteredamounts of first and second chemical reactants into the mixing chamberto form a reaction mixture so that the chemical reactants undergo anexothermic chemical reaction to generate heat and one or more reactionproducts; an electronic control device linked to the dispensing meansfor controlling the dispensing of the metered amounts of first andsecond chemical reactants; one or more pumps for moving the chemicalreactants and reaction mixture around the apparatus; a heat exchangerhaving an inlet and an outlet for the reaction mixture and an inlet andan outlet for the said liquid, so that when said liquid passes throughthe heat exchanger it is heated by heat transfer from the reactionmixture; one or more monitoring stations for monitoring one or morephysical or chemical parameters of the reaction mixture; the monitoringstations being arranged to communicate with the electronic controldevice; and a waste outlet for removing spent reaction mixture from theapparatus; wherein the mixing chamber, heat exchanger and the one ormore monitoring stations are connected so as to form a loop; and whereinthe electronic control device is programmed to cause the reactionmixture to be circulated around the loop at least twice, and optionallyto cause the dispensing means to dispense further metered amounts offirst and/or second chemical reactants into the mixing chamber; and/orto cause a proportion of the reaction mixture to be ejected through thewaste outlet, in order to control the temperature of the reactionmixture passing through the heat exchanger.
 43. An apparatus accordingto claim 42 wherein one of the said one or more monitoring stations formonitoring one or more physical or chemical parameters of the reactionmixture is located downstream of the mixing chamber and upstream of theheat exchanger.
 44. An apparatus according to claim 43 wherein anin-line mixer is interposed between the monitoring station and the heatexchanger.
 45. An apparatus according to claim 42 wherein one of thesaid one or more monitoring stations for monitoring one or more physicalor chemical parameters of the reaction mixture is located downstream ofthe heat exchanger and upstream of the mixing chamber.
 46. An apparatusaccording to claim 45 wherein an in-line mixer is located in the loopdownstream of the monitoring station and upstream of the mixing chamber.47. An apparatus according to claim 42 wherein the one or more physicalor chemical parameters monitored by the said one or more monitoringstations are selected from the pH, temperature, flow rate and viscosityof the reaction mixture.
 48. An apparatus according to claim 42comprising a second heat exchanger, the second heat exchanger beinglocated externally of the loop and upstream of the dispensing means, andhaving an inlet and an outlet for the first chemical reactant and aninlet and an outlet for the second chemical reactant, so that heat maybe exchanged between the first and second chemical reactants withoutmixing of the reactants.
 49. An apparatus according to claim 48 whereina mixer is provided upstream of the second heat exchanger, and dosingmeans are provided for introducing into the mixer one of the first andsecond reactants and a solvent therefor.
 50. An apparatus according toclaim 42 wherein storage containers are provided for storing the firstand second chemical reactants, wherein the storage containers are influid communication with the dispensing means and, where present, thesecond heat exchanger.
 51. An apparatus according to claim 42 whereinthe electronic control device is programmed to cause the reactionmixture to be circulated around the loop between two and ten times. 52.An apparatus according to claim 42 wherein the electronic control deviceis programmed to cause the dispensing means to dispense one or morefurther doses of the first and/or second reactants if the temperature ofthe reaction mixture falls below a predetermined value.
 53. An apparatusaccording to claim 42 wherein the first chemical reactant is an acid andthe second chemical reactant is a base and the electronic control deviceis programmed (i) to cause the dispensing means to dispense one or morefurther doses of the acid if the pH of the reaction mixture exceeds apredetermined value; or (ii) to cause the dispensing means to dispenseone or more further doses of the base if the pH of the reaction mixturefalls below a predetermined value.
 54. An apparatus according to claim42 wherein the electronic control device is programmed to provide aflushing step at the end of a predetermined period of heating, theflushing step serving to flush out of the apparatus any residualreaction mixture, and further wherein the electronic control device isprogrammed to provide a drainage step following the flushing step. 55.An apparatus according to claim 42 wherein the first reactant isaluminium and the second reactant is an alkali metal hydroxide.
 56. Anapparatus according to claim 55 wherein the aluminium is in powder form.57. An apparatus according to claim 55 wherein the alkali metalhydroxide is sodium hydroxide.
 58. An apparatus according to claim 42wherein the liquid to be heated is water.
 59. An apparatus according toclaim 42 which forms part of a domestic water heating system or anindustrial or commercial water heating system.
 60. An apparatusaccording to claim 59 wherein the water heating system provides waterfor central heating or sanitation purposes.
 61. An apparatus for heatinga liquid, which apparatus comprises: a first storage containercontaining a first chemical reactant which comprises aluminium in powderform; a second storage container containing a second chemical reactantwhich comprises an alkali metal hydroxide; a mixing chamber; dispensingmeans for dispensing metered amounts of the first and second chemicalreactants the first and second storage containers into the mixingchamber to form a reaction mixture so that the undergo an exothermicchemical reaction to generate heat and reaction products, one of thereaction products being hydrogen gas; an electronic control devicelinked to the dispensing means for controlling the dispensing of themetered amounts of first and second chemical reactants; one or morepumps for moving the chemical reactants and reaction mixture around theapparatus; a heat exchanger having an inlet and an outlet for thereaction mixture and an inlet and an outlet for the said liquid, so thatwhen said liquid passes through the heat exchanger it is heated by heattransfer from the reaction mixture; one or more monitoring stations formonitoring one or more physical or chemical parameters of the reactionmixture; the monitoring stations being arranged to communicate with theelectronic control device; a waste outlet for removing one or morenon-gaseous reaction products from the apparatus; and an outlet forremoving hydrogen gas from the apparatus; wherein the mixing chamber,heat exchanger and the one or more monitoring stations are connected soas to form a loop; and wherein the electronic control device isprogrammed to cause the reaction mixture to be circulated around theloop at least twice, and optionally to cause the dispensing means todispense further metered amounts of first and/or second chemicalreactants into the mixing chamber; and/or to cause a proportion of thereaction mixture to be ejected through the waste outlet, in order tocontrol the temperature of the reaction mixture passing through the heatexchanger.